Process for the non-aqueous continuous dyeing and printing of fibre material made from synthetic polyamide

ABSTRACT

A process for the non-aqueous, continuous dyeing or printing of synthetic polyamide fibre material is disclosed, which comprises impregnating or printing this material with a solution of at least one dye salt consisting of the anionic radical of an anionic dyestuff and the cationic radical of an isothiourea derivative capable of salt formation, in a halogenated aliphatic hydrocarbon, optionally containing thickener, on its own or in admixture with a liquid, water-soluble organic solvent, removing excess dye liquor from the material and fixing the dyestuff by a heat treatment of the impregnated or printed fibre material at temperatures below the softening point of the fibre material, thereby obtaining a finished dyeing or print on said fibre material. By this process, on the stated fibre material are obtained deeply coloured, even and well developed dyeings having good fastness properties, such as fastness to wet processing, rubbing and dry cleaning.

United States Patent [1 1 Wegmuller et al.

[ Jan. 22, 1974 [75] Inventors: Hans Wegmuller, Riehen; Alois Kleemann, Basel, both of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Apr. 9, 1971 21 App]. No.: 132,809

[30] Foreign Application Priority Data Apr. 10, 1970 Switzerland 5312/70 {52] US. Cl. 8/172, 8/173 [51] Int. Cl D06]! 1/68 [58] Field of Search 8/172, 173, 174, 6, 84, 85

[56] References Cited UNITED STATES PATENTS 3,510,243 5/1970 Seuret et al 8/39 2,922,690 l/l960 Mueller et al. 8/21 A 3,657,220 4/1972 Kilmurry 8/4 B X 2,349,282 5/1944 Kern 8/6 X FOREIGN PATENTS OR APPLICATIONS 340,572 12/1930 Great Britain 8/6 l,24l,899 8/l97l Great Britain 8/94 OTHER PUBLICATIONS Colur Index, Vol. 2, 2nd Ed., 1956, pp. 2815-2816, Pub]. AATCC Primary ExaminerLeon D. Rosdol Assistant ExaminerT. J. Herbert, Jr. Attorney, Agent, or Firm-Wenderoth, Lind & Ponack 5 7 ABSTRACT A process for the non-aqueous, continuous dyeing or printing of synthetic polyamide fibre material is disclosed, which comprises impregnating or printing this material with a solution of at least one dye salt consisting of the anionic radical of an anionic dyestuff and the cationic radical of an isothiourea derivative capable of salt formation, in a halogenated aliphatic hydrocarbon, optionally containing thickener, on its own or in admixture with a liquid, water-soluble organic solvent, removing excess dye liquor from the material and fixing the dyestuff by a heat treatment of the impregnated or printed fibre material at temperatures below the softening point of the fibre material, thereby obtaining a finished dyeing or print on said fibre material. By this process, on the stated fibre material are obtained deeply coloured, even and well developed dyeings having good fastness properties, such as fastness to wet processing, rubbing and dry clean- 12 Claims, No Drawings PROCESS FOR THE NON-AQUEOUS CONTINUOUS DYEING AND PRINTING OF FIBRE MATERIAL MADE FROM SYNTHETIC POLYAMIDE DETAILED DISCLOSURE The present invention relates to a process for the non-aqueous, continuous dyeing and printing of fibre material made from synthetic polyamide, to the dye solutions usable for this purpose, as well as to the fibre material dyed or printed according to this process.

It has been found that deeply coloured and fast dyeings and printings can be produced on fibre material made from synthetic polyamide by impregnating or printing the fibre material with the solution of at least one dye salt consisting of the anionic radical of an anionic dyestuff and the cationic radical of an isothiourea derivative capable of salt formation in a halogenated aliphatic hydrocarbon, optionally containing thickeners, on its own or in admixture with a liquid watersoluble organic solvent; removing an appreciable part of the excess solvent from the material, and fixing the dyeing or the printing by a heat treatment at temperatures below the softening point of the fibre material.

Suitable isothiourea derivatives capable of salt formation, are, in particular, those of formula I:

wherein R,, R and R each represent, independently of each other, hydrogen, an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical, whereby R and R together with the group can also form the radical of a partially saturated ring, and

B represents an unsubstituted or substituted alkyl or alkenyl group having one to 18 carbon atoms in the main chain, which can be interrupted by hetero atoms; a cycloalkyl or an unsubstituted or substituted aralkyl radical.

lsothiourea derivatives of formula I are known per se and can be produced by known methods.

If R R and/or R in formula I represent an aliphatic hydrocarbon radical, then they represent, in particular, unsubstituted lower alkyl groups having advantageously one to four carbon atoms, such as the methyl, ethyl, isopropyl, or tert.butyl groups. Suitable as cycloaliphatic hydrocarbon radicals denoted by R,, R and R is, e.g. the cyclohexyl group. If R,, R and R represent an araliphatic hydrocarbon radical, then this preferably contains seven to nine carbon atoms, such .as the phenethyl group, and especially the benzyl group. If R,, R and/or R denote an aromatic hydrocarbon radical, then this can be, e.g. an unsubstituted or substituted phenyl radical, whereby suitable substituents are halogen such as chlorine or bromine, lower alkyl or lower alkoxy groups preferably containing one or two carbon atoms.

If R and R together with the groups form the radical of a partially saturated ring, then this concerns, in particular, diazole or diazine rings. Examples in this case are the A -imidazolinyl group or the A -tetrahydropyri-midinyl group.

As unsubstituted or substitute alkyl or alkenyl groups having one to 18 carbon atoms in the main chain, B represents a straightchain or branched alkyl or alkenyl group, which as substituents can contain, e.g. the hydroxyl group, a lower alkoxy group such as the methoxy or ethoxy group, or a phenoxy group, such as the methyl, ethyl, isopropyl, amyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadec-9-enyl, B-hydroxyethyl, B-methoxyethyl, B-ethoxyethyl, B-phenoxyethyl, or l2-hydroxyoctadec-9-enyl group. If the main chain of the alkyl or alkenyl group B is interrupted by hetero atoms, then particularly suitable are chains interrupted by oxygen atoms. Mentioned as examples of such groups are the B-dodecyloxyethyl group and ,B-octadecenyloxyethyl group.

As a cycloalkyl radical, B denotes, in particular, the cyclohexyl radical. Mentioned as examples of unsubstituted or substituted aralkyl radicals represented by B are the phenethyl radical, and, in particular, the benzyl radical which may be substituted by alkyl groups having one to 10 carbon atoms, or halogen, especially chlorine.

On account of the therewith obtainable dyestuffs particularly readily soluble in solvents or in mixtures of solvents usable according to the invention, isothiourea derivatives of formula I are preferred wherein R,, R and R each represent, independently of each other, hydrogen or an unsubstituted alkyl radical having one to four carbon atoms, and B denotes an unsubstituted alkyl or alkenyl radical having eight to 18 carbon atoms, such as the octyl, decyl, dodecyl, octadecyl, or octadec-9-enyl group, or the benzyl group.

Suitable halogenated, especially chlorinated, aliphatic hydrocarbons are, e.g. chloroform, carbon tetrachloride, trifluoro-trichloroethane, dichloroethane, trichloroethane, tetrachloroethane, dibromoethylene, dichloropropane, trichloropropane, pentachloropropane, chlorobutane, dichlorobutane or dichlorohexane, and especially trior tetrachloroethylene (perchloroethylene). Also mixtures of such solvents may be used.

In certain cases, the use of a solvent mixture consisting of 50 to 99 per cent by weight, preferably to 99 per cent by weight, of halogenated, preferably chlorinated lower aliphatic hydrocarbon and 50 to l per cent by weight, preferably 20 to 1 per cent by weight, of a liquid water-soluble organic solvent has proved advantageous.

By liquid, water-soluble organic solvents are meant thermostable solvents which are soluble in water not only to the extent of fractions of one per cent but to the extent of several per cent. Examples of such solvents are higher alkanols such as butanols or amyl alconol, ethanol, nor iso-propanol; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl or -ethyl ether; then also furfuryl or tetrahydrofurfuryl alcohol, or bivalent aliphatic alcohols such as ethylene glycol or 1,2-propylene glycol; also lower aliphatic ketones such as acetone, lower cyclic ethers such as dioxane; also N,N-dialkylamides of lower monocarboxylic acids such as dimethylformamide or dimethylacetamide, amides of carbonic acid such as N,N,N,N'- tetramethylurea, cyclic amides such as N-methylpyrrolidone, as well as mixtures of such liquid, watersoluble organic solvents.

Preferred solvent mixtures consist of 90 to 99 per cent by weight of trichloroethylene, perchloroethylene, or trichloroethane, and to 1 per cent by weight of a lower alkanol such as methanol, or of an N,N-dialkylamide of lower monocarboxylic acids such as dimethylacetamide or dimethylformamide.

When selecting a solvent or solvent mixture, it is to be ensured that, with the attainment of the optimum dyeing effect, no damage, or the smallest possible damage, thereby occurs to the fibres.

Anionic dyestuffs usable according to the invention can belong to the most diverse classes such as, e.g. to those of the oxazine, triphenylmethane, xanthene, nitro, methine, quinophthalone, acridone, or phthalocyanine dyestuffs, especially, however, to the class of metallised and metal-free mono-, disor polyazo dyestuffs, and to the class of anthraquinone dyestuffs or copperphthalocyanine dyestuffs. Of the stated nonmetallised azo and anthraquinone dyestuffs, those are preferred which contain one or two sulphonic acid groups. Suitable metal complex azo dyestuffs are, e.g. such ones which contain to one metal atom two azo dyestuff molecules. Suitable metal atoms are, in particular, chromium or cobalt. These lz2-metal complexes can moreover be free of acid water-solubilising groups such as carboxylic acid groups, and especially sulphonic acid groups, and can contain, in their place, alkyl-sulphonyl or sulphamoyl groups. Surprisingly, also with such la2-metal complexes are obtained by the process according to the invention particularly deeply coloured and fast dyeings. Also mentioned are the formazane dyestuffs containing as the metal atom, in particular, copper, but also nickel.

The production of the dye salts from the anionic dyestuff and the isothiourea derivative capable of salt formation can be performed in situ, i.e. in the solvent or solvent mixture itself. Preferably, however, the dye salts are produced in a manner known per se beforehand, and then added to the solvent or solvent mixture. The preparation of the dye salts can thereby be effected, e.g. by double reaction, advantageously in the heat, by reacting the alkali metal salt or ammonium salt, especially the sodium salt, of the anionic dyestuff with the salt of an isothiourea derivative usable according to the invention with a strong acid, e.g. hydrochloric acid. Optionally, the desired dye salts can be produced direct by neutralisation of the anionic dyestuffs in the form of their free acids with the isothiourea derivatives. If the dye salts are produced in situ, then the anionic dyestuffs are advantageously used likewise in the form of their alkali metal salts or ammonium salts, especially in the form of their sodium salts.'Also the isothiourea derivative is thereby advantageously used in the form of a salt with a strong acid. In this case it is advantageous, if the prepared dye liquor still contains insoluble constituents, to clear the liquor of insoluble substances, e.g. by filtration, before the fibre material to be dyed or printed is introduced.

lf anionic dyestuffs are used which can form doubly or multiply negatively charged anions, it is in many cases not necessary for these charges to be completely compensated by the isothiourea derivative.

The dye solution to be used according to the invention preferably contains, depending on the desired depth of colour, 0.1 to 30 per cent by weight, calculated on the weight of the material to be dyed, of one or several of the dye salts defined hereinbefore.

if necessary, the dye solution usable according to the invention may also contain thickeners, advantageously such thickeners which are soluble in the solvent or solvent mixture as defined, e.g. ethyl cellulose.

Suitable fibre materials made from synthetic polyamide which can be dyed or printed according to the invention are, in particular, polyhexamethyleneadipamide (Polyamide 6.6, Nylon), polycaprolactam (Polyamide 6, Perlon) and polyaminoundecanoic acid (Polyamide l l, Rilsan), especially in the form offilament; also textured synthetic polyamide fibres such as Banlon. The stated fibre materials can be dyed or printed according to the invention in any desired form, e.g. in the form of flock, slubbing, yarn, or preferably fabrics.

The continuous impregnation of the fibre material is effected, for example, by printing or spraying,preferably, however, by pad dyeing. In the last-mentioned case, the fibre material is advantageously passed at room temperature continuously through the dye solution, and afterwards squeezed out to obtain the desired content of impregnating solution of approximately 30 to 150 per cent by weight (relative to the dry weight of the material). The main proportion of the solvent or solvent mixture remaining in the fibre material is adv antageously subsequently removed under mild conditions at 40 to C, especially in a warm dry air stream.

Fixing of the dyestuff on the still moist or already dry fibre material, from which the excess dye liquor has been removed, is carried out, e.g. by steaming in water vapour or solvent vapour, preferably, however, by a dry heat treatment below the softening point of the fibre material. It is also possible to combine these two forms of heat treatment. A suitable dry heat treatment consists in exposing the material to the action of high frequency alternating currents, or to infra-red rays; preferably, however, fixing of the dyestuff on the fibre material is effected in a hot air stream and, in particular, by means of contact heat at to 230C, especially at a temperature of 190 to about 220C, for 60 to 180 seconds.

Using the process according to the invention are obtained on the stated fibre material, even deeply coloured, and, without any aftertreatment, fast dyeings, e.g. dyeings fast to dry cleaning, washing, perspiration and rubbing.

ln comparison to the use of the alkali salts, especially sodium salts of the corresponding anionic dyestuffs, the use according to the invention of the isothiourea dye salts as defined promotes, on heat treatment, the diffusion of the dye salts into the fibres, in consequence of which the colour strength is increased and the fastness properties of the thereby obtained dyeings or printings are in many cases improved.

A special advantage of the process according to the invention is that it is particularly suitable for the dyeing and printing of fibre material made from synthetic polyamide using mixtures of dye salts of anionic dyestuffs of various classes, e.g. mixtures of the isothiourea dye salts of the above mentioned 1:2-metal complex dyestuffs, containing alkylsulphonyl and/or sulphamoyl groups, with isothiourea dye salts of metal-free dyestuffs containings sulphonic acid groups. Thereby are obtained, in most cases, in contrast to dyeings obtained from a procedure using a mixture of the corresponding anionic dyestuffs from an aqueous medium, very even dyeings.

Temperatures are given in C in the following examples.

H I I A NHz k/ and 3.0 g of S-benzyl-isothiourea-chlorohydrate are dissolved in lOO g of ethanol. The obtained solutionis afterwards diluted with 900 g of trichloroethylene. The slight amounts of precipitated material are removed by filtration of the solution.

With the thus prepared dark-blue-coloures, clear dye salt solution is impregnated a fabric made from Polyamide 6.6 or 6; the material is then squeezed out to ca.

EXAMPLE 2 An @1099. Q qsp hesis 592 h formula Hnc CH: '6 I- o-Gm 111 l S02 K/ N=N J) NH-IGB 1' CuH15-SC\ ---H l NIL-l N=N *ik/ c N\ LH O Hlo CH:

EXAMPLE 3 7 An amount of 10 g of the dye salt of the formgla is dissolved in a solvent mixture consisting of 920 g of trichloroethylene and 70 g of methanol. With the obtained solution is impreganted a knitted fabric made from Polyamide 6, as described in Example 1. The impreganted knitted fabric is afterwards thermofixed dur- 80 percent liquor absorptiomrelative to the dry weight of the material. The impregnated fabric is subsequently dried at 50 in an air stream, and then heated for seconds to 200.

In this manner are obtained well developed even, deeply coloured, blue dyeings having very good fastness to rubbing, to perspiration, and to dry clearing fgmula (IJH:

NBOzS II N le 99 essat 99.1.

Thus obtained is a deeply coloured, even and well de- L'PBEQEAQQ EQP the ebe ss mat r l,

The above dye salt is obtained, for example, as follows: An amount of 10.8 g of the dyestuff of the forl N II N OH NH: HzN

SOiNa 7 22" In 1000 ml of water at 50 are then separately dissolved 5.6 g of S- dodecylisothiourea-chlorohy drate. The two solutions are combined, resulting in the immediate formation of a red precipitate in a finely dispersed form. To the still warm dispersion are then added, with stirring, 40 g of sodium chloride, and the reaction mixture is allowed to stand for one to two days at room temperature. After this period of time, the dye salt has practically completely settled out. The colourless solution on top is decanted off; the sediment is filtered off under suction and then dried in vacuo at 5060. In this manner are obtained l2.2 g of the dye salt of the formula given in the first paragraph of this example, the dye salt being i tbs o mo LSQHUMQDBQ- A- EXAMPLE 4 fim q tsf lOiQfLh dy l ftheformuli a S OiNHCHICHjOH-[CHHM- TABl.E l

Example Water-miscihlc solvents No.

5 ethanol 6 isopropanol II l2 l3 If in the Example 4 to 13 is used, instead of 900 g of trichloroethylene, the same amount of one of the halogenated hydrocarbons listed in the following Table ll, Column 2, with otherwise the same procedure as given in this example, then likewise are obtained even and lL lqlq qd y ins TABLE ll Example Halogenalcd hydrocarbon 3 No.

l4 trifluorotrichlorocthanc l5 trichloroethane l6 tetrachloroethylcnc AMPl llM A". e nqum f J2; f t e. qysi ltq fqt u H3O CH;

N lo.

.8 NH ea Q T CHrS--C ---H O NH H; C CH1 Thus obtained is a deeply coloured, even and well developed blue dyeing having good fastness to rubbing, to water, and to dry cleaning. lf, instead of a fabric made from Polyamide 6.6, a fabric or knitted material made from Polyamide 6 is used, with otherwise the same procedure as described in the example, then likewise is obtained a deeply coloured and well developed blue dyeing having good fastness to rubbing 7 If, in the above example, the 90 g of methanol are replaced by the same amount of one of the solvents listed in the following Table l, Column 2, with otherwise the same procedure as described in the example, then blue dyeings are obtained of equal quality,

is dissolved in a solvent mixture consisting of 920 g of an appreciably weaker dyeing is obtained.

EXAMPLE 18 An amount of 10 g of the dye salt of the formula W CHa aw- 43 NHI Thus obtained is a deeply coloured, even and well de- 15 veloped yellow dyeing having good fastness to rubbing,

to WW5 nd to dry havin lf, instead of the dye salt given in the above example, the same amount of one of the dye salts listed in the fol- 20 lowing Table Ill, Column 2, is used, the procedure being otherwise as described above, then likewise are obtained deeply coloured dyeings of Polyamide 6.6 in the shades given in the last column of the table.

TABLE 111 Example Shade on P yamide 6.6

number Dye salt 19 O NHOH(CH3)3 0 NH-Q-CH;

20 C2HsO2S NH Yellow.

(JO-CH: CnHzg-B-C --H N=N- H J NH /C-NH l c1 /CNH N=NCH 0-CH: (kHz-0:

21 NE (a Green.

i l l X CnH2s--SC H A we J O NH Y SOaNa 0 -Q- -U 22 Yellow.

TABLE III-Continued Example number Dye salt H e qTJ HE H mm m HH H mm m HH H N N C s h. H m H w H C [L X m r! IIIN N| 1 1 H m SIOI. Wm.

Blue.

CHr-S-C CH NHC 0- 3,787,1 89 1; 14 TABLE IIL-Continued Shadeon Example polyd number Dye salt 55 e 30 CH2 N.--CH2 9 DO- I I e SO39 X CHaOCHzCHzS-C /CH2-H NH-CHz .l

OH, I I CHzNHCO.-@ O NH CH:

31 O CH: NH 6 Do.

I I H O H 'H S H SO36 X C12 25 C z- ---C\ I OH; I CH2NHCO O NH- CH:

Illa

A M .lZAMEEE 3L N=NCCH| i i An amount of g of the dye salt of the formula 0, NH 9 is dissolved in a solvent mixture consisting of 900 g of 3 EN T C H S C% 1 trichloroethylene and 70 g of dimethylacetamide. A 01 M '5 I fabric made from Polyamide 6.6 is impregnated at NH room temperature with the thus obtained clear yellow 30 6 dye salt solution; the impregnated fabric is squeezed out to obtain a liquor absorption of ca. 80 percent, relative to the dry weight of the material, and is then dried at 40-80 in an air stream. The fabric is afterwards thermofixed for 90 seconds at 210 by the action of 35 contact heat.

II N absorption of 80 percent, the impregnated fabric is dried in a hot air stream at 80, and afterwards there.....em f .xedf s con M200",

EXAMPLE 33 An amount of 10 g of the dye salt of the formula is dissolved in 990 g of trichloroethylene. With the obtained solution is impregnated a fabric made from Polyamide 6. After being squeezed out to obtain a liguor In this manner is obtained a deeply coloured, even and well developed yellow dyeing having good fastness to rubbing.

Similarly good results are obtained if the fabric, in stead of being thermofixed for 90 seconds at 200, is steamed for 5 minutes with superheated perchloroethylene vapour at l40-l50.

EXAWEEii...

In a solvent mixture consisting of 915 g of trichloroethylene and g of methanol are dissolved 3.5 g of the dyeseltgfwthe rmu V Nil l9 NO: CHI

2 g. of the dye salt of the formula /C=N 'oiN--N=Nc 0 NH-|o Or oiiHi,-s c H 0\ NHLI Q G 1 ON N=NC C=N JHa l as well as 10 g. of the dye salt of the formula NH ea Q Q h l CHiNHCO CHz-SC H Y J NH -CH, NH

With the obtained clear dark grey dye salt solution is can also form the radical of a partially saturated ring, impregnated at room temperature fabric made from and Polyamide 6.6; the impregnated fabric is squeezed out represents an unsubstituted or substituted alkyl or alto obtain a liquor absorption of 70 percent, relative to kenyl group having 1 to 18 carbon atoms in the the dry weight of the material, and then dried at main chain, which can be rr p y hetero 40-80 in an air stream. The fabric is afterwards theratoms; a cycloalkyl or an unsubstituted or imofixed for 90 seconds at 210 by the action of contact tuled r lkyl rad a heat. I. in a solvent selected from halogenated aliphatic hy- Thus obtained is a deeply coloured, even and well dedI'OCaTbOh, 0r veloped grey dyeing having good fastness to rubbing, to in a HI miXtur whi Consists f water, and to dry cleaning. 40 a. halogenated aliphatic hydrocarbon and If, i t d f a f b i d f P id 6.6 a 3. a liquid water-soluble, organic solvent selected from fabric or knitted article made from Polyamide 6 is used, the group Consisting of alkanols, cycloaliphatic 3160' the procedure being otherwise as described in the artihols, araliphatic alcohols, aliphatic and cycloaliphatic cle, then likewise is obtained a deeply coloured and ketohes, alkylene glycol monoalkyl i ful'furyl well develo d grey d i h i d f t to echo], tetrahydrofurfuryl alcohol, divalent aliphatic albing. cohols, lower cyclic ethers, N,N-dialkylamides of lower monocarboxylic acids, amides of carbonic acid and We claim: l. A process for the non-aqueous, continuous dyeing EX L L or printing of synthetic polyamide fibre material, which removing a supstamial P of excess y liquor comprises: from the material, and

a. impregnating or printing synthetic polyamide fibre fixing the dyesluff by a heat tratmem of the material with a solution of at least one dye salt conpregnated or pnmed fibre mammal at temperatures sisting of the anionic radical of an anionic dyestuff 1 i Q F PL 3 h fibre z and the cationic radical of an isothiourea derivative t ere y o tammg a 6 yemg or prmt on t e a bl of R f f m f said fibre material. 7, V c pa e S? ee omjulal" 2. A process as described in claim I, further compris- R1 ing (lll) thickener admixed with said solvent (l) or sol-.

N vent mixture (ll).

3. A process as described in claim 1, wherein the sol- (,0 vent defined under (I) consists of chlorinated lower ali- Rz-N phatic hydrocarbon. Where"! 4. A process as described in claim 1, wherein said soln 2 and 3 each pr n independently of each vent is trichloroethylene or tetrachloroethylene.

y g an aliphatic, cycloaliphatic, arflli- 5. A process as described in claim 1, wherein the solphatrc, or aromatic hydrocarbon radical, whereby vent mixture defined under (ll) consists of R and R together with the group 7 a. 50 to 99 percent by weight of halogenated lower aliphatic hydrocarbon, the balance consisting of B. a liquid, water-soluble organic solvent selected from the group consisting of alkanols, cycloali- L W phatic alcohols, araliphatic alcohols, aliphatic and l7 cycloaliphatic ketones, alkylene glycol monoalkyl ethers, furfuryl alcohol, tetrahydrofurfuryl alcohol, divalent aliphatic alcohols, lower cyclic ethers, N,N-dialkylamides of lower monocarboxylic acids, amides of carbonic acid and mixtures thereof.

6. A process as described in claim 5, wherein the water-soluble organic solvent defined unter (H3) is selected from the group consisting of methanol, ethanol, n.propanol, isopropanol, butanols, pentanols, cyclohexanol, benzyl alcohol, acetone, methylethyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylenev glycol, dioxane, dimethylformamide, dimethylacetamide, N,N,N',N-tetramethyl urea, and mixtures of such solvents.

7. A process as described in claim 1, wherein the solvent mixture defined unter (ll) consists of 80 to 99 percent by weight of a chlorinated, lower aliphatic hydrocarbon, the balance consisting of a water-soluble organic solvent.

8. A process as described in claim 1, wherein the solvent mixture defined under (ll) consists of 90 to 99 percent by weight of trichloroethylene, perchloroethylene or trichloroethane, the balance consisting of methanol, dimethylacetamide or dimethylformamide.

9. A process as described in claim I, wherein the imprenated or printed material is subjected to a dry heat treatment.

10. An organic non-aqueous dye liquor comprising A. a halogenated aliphatic hydrocarbon on its own or in admixture with a liquid, water-soluble organic solvent, and (B) a dye salt consisting of the anionic radical of an anionic dyestuff and the cationic radical of an isothiourea derivative capable of salt formation of the formula can also form the radical of a partially saturatedring, and

represents an unsubstituted or substituted alkyl or alkenyl group having one to 18 carbon atoms in the main chain, which can be interrupted by hetero atoms; a cycloalkyl or an unsubstituted or substituted aralkyl radical. 11. An organic non-aqueous dye liquor as described in claim 10, comprising C. thickener in admixture with said mixture of (A) and (B). 12. A process as described in claim 1 wherein the isothiourea derivative is of the formula whrih" R,, R and R each represent, independently of the other, hydrogen, lower alkyl of one to four carbon atoms, cycloalkyl of up to six carbon atoms, phenyl lower alkyl of seven to nine carbon atoms, phenyl, phenyl substituted by a member of the group (a) chlorine, (b) bromine, (c) lower alkyl of one to two carbon atoms and (d) lower alkoxy of one to two carbon atoms, or R and R together with the group forma diaz ole or a diaai ne r ing, and

B represents (a) straight or branched chain alkyl or alkenyl of one to 18 carbon atoms, (b) substituted straight or branched chain alkyl or alkenyl of one to 18 carbon atoms wherein the substituents are selected from the group of hydroxy, lower alkoxy and phenoxy, (c) straight or branched chain alkyl or alkenyl of one to l8.carbon atoms wherein the main chain is interrupted by an oxygen atom, (d) cycloalkyl of up to six carbon atoms, (e) phenyl lower alkyl, or (f) phenyl lower alkyl substituted by a member'of the group of alkyl of one to H) carbon atoms and chlorine. 

2. A process as described in claim 1, further comprising (III) thickener admixed with said solvent (I) or solvent mixture (II).
 3. A process as described in claim 1, wherein the solvent defined under (I) consists of chlorinated lower aliphatic hydrocarbon.
 4. A process as described in claim 1, wherein said solvent is trichloroethylene or tetrachloroethylene.
 5. A process as described in claim 1, wherein the solvent mixture defined under (II) consists of Alpha . 50 to 99 percent by weight of halogenated lower aliphatic hydrocarbon, the balance consisting of Beta . a liquid, water-soluble organic solvent selected from the group consisting of alkanols, cycloaliphatic alcohols, araliphatic alcohols, aliphatic and cycloaliphatic ketones, alkylene glycol monoalkyl ethers, furfuryl alcohol, tetrahydrofurfuryl alcohol, divalent aliphatic alcohols, lower cyclic ethers, N,N-dialkylamides of lower monocarboxylic acids, amides of carbonic acid and mixtures thereof.
 6. A process as described in claim 5, wherein the water-soluble organic solvent defined unter (II Beta ) is selected from the group consisting of methanol, ethanol, n.propanol, isopropanol, butanols, pentanols, cyclohexanol, benzyl alcohol, acetone, methylethyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, dioxane, dimethylformamide, dimethyl-acetamide, N,N,N'', N''-tetramethyl urea, and mixtures of such solvents.
 7. A process as described in claim 1, wherein the solvent mixture defined unter (II) consists of 80 to 99 percent by weight of a chlorinated, lower aliphatic hydrocarbon, the balance consisting of a water-soluble organic solvent.
 8. A process as described in claim 1, wherein the solvent mixture defined under (II) consists of 90 to 99 percent by weight of trichloroethylene, perchloroethylene or trichloroethane, the balance consisting of methanol, dimethylacetamide or dimethylformamide.
 9. A process as described in claim 1, wherein the imprenated or printed material is subjected to a dry heat treatment.
 10. An organic non-aqueous dye liquor comprising A. a halogenated aliphatic hydrocarbon on its own or in admixture with a liquid, water-soluble organic solvent, and (B) a dye salt consisting of the anionic radical of an anionic dyestuff and the cationic radical of an isothiourea derivative capable of salt formation of the formula
 11. An organic non-aqueous dye liquor as described in claim 10, comprising C. thickener in admixture with said mixture of (A) and (B).
 12. A process as described in claim 1 wherein the isothiourea derivative is of the formula 